CN1875507A - Electrode active material and use thereof - Google Patents
Electrode active material and use thereof Download PDFInfo
- Publication number
- CN1875507A CN1875507A CNA2004800323106A CN200480032310A CN1875507A CN 1875507 A CN1875507 A CN 1875507A CN A2004800323106 A CNA2004800323106 A CN A2004800323106A CN 200480032310 A CN200480032310 A CN 200480032310A CN 1875507 A CN1875507 A CN 1875507A
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- Prior art keywords
- active material
- electrode active
- metal complex
- sub
- amorphous
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- 239000007772 electrode material Substances 0.000 title claims description 71
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- -1 e.g. Inorganic materials 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000005300 metallic glass Substances 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 150000003624 transition metals Chemical class 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 238000001228 spectrum Methods 0.000 claims description 10
- 150000002642 lithium compounds Chemical class 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000011263 electroactive material Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 abstract description 4
- 238000003701 mechanical milling Methods 0.000 abstract description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000002427 irreversible effect Effects 0.000 description 30
- 238000007599 discharging Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 229910021532 Calcite Inorganic materials 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
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- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 230000004927 fusion Effects 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical class CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
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- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates containing plural metal or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
An electroactive material and a method of manufacturing the same is provided, in which the primary component of the electroactive material is a metal boron oxide complex, and the electroactive material exhibits excellent charge/discharge characteristics. The electroactive material of the present invention is primarily composed of an amorphous metal complex represented by the general formula M<SUB>2-2x</SUB>B<SUB>2x</SUB>O<SUB>3</SUB>. M is one or two or more metal elements selected from the transition metal elements, e.g., Fe or V. In addition, x is 0<x<1, e.g., 1/2 . This type of electroactive material can be manufactured by amorphizing the metal complex represented by the general formula M<SUB>2-2x</SUB>B<SUB>2x</SUB>O<SUB>3 </SUB>by means of a mechanical milling method. In addition, the electroactive material can be manufactured by rapidly cooling and solidifying a mixture containing an oxide in which M is a constituent metal element and a boron oxide from the melted state.
Description
The present invention advocates the priority of the 2003-373358 Japanese patent application that on October 31st, 2003 proposed, and the full content of this application is introduced in this specification as reference.
Technical field
The present invention relates to be suitable as the electrode active material (ElectroactiveMaterial) and the manufacture method thereof of the constituent material of battery.In addition, the invention still further relates to the secondary cell that uses the kind electrode active material.
Background technology
Have a kind of like this secondary cell known, its cation by lithium ion etc. is realized discharging and recharging moving of two interpolars.For example lithium rechargeable battery is the exemplary of such secondary cell.As the electrode active material of such secondary cell, can adopt the material that can absorb and discharge lithium ion.For example the material with carbon element of graphite etc. can be used as negative electrode active material.For example lithium nickel type oxide, lithium-cobalt oxide etc. serves as that the oxide (hereinafter referred to as " lithium-contained composite oxide ") that constitutes element can be used as positive active material with lithium and transition metal.
From the angle of high performance, high capacity and the cost degradation of such secondary cell, studying various materials as positive electrode active materials and negative active core-shell material.For example, open the spy and to have recorded and narrated a kind of like this electrode active material in the flat 10-134813 communique, it is with general formula FeBO
3Represented iron complex is a main body.In addition, as other prior art, open the spy and also to disclose corresponding techniques in the 2003-157841 communique about the electrode active material that will constitute by the metal perborate complex compound.Therefore, if a kind of electrode active material of borate family can be provided, it can realize better battery behavior, will be very useful.
The object of the present invention is to provide a kind of electrode active material based on the metal perborate complex compound, it can bring into play good battery behavior (for example charge-discharge characteristic).Another object of the present invention is to provide a kind of manufacture method of such electrode active material.And then another object of the present invention is to provide a kind of rechargeable nonaqueous electrolytic battery with kind electrode active material.Be as another purpose that is associated, electrode for cell and manufacture method thereof with kind electrode active material are provided.
Summary of the invention
Inventor of the present invention finds, in the electrode active material based on the metal perborate complex compound, by adopting amorphous complex compound, battery behavior is improved, and sets out thus and has finished the present invention.
The invention provides a kind of with by formula M
2-2xB
2xO
3Represented metal complex is the electrode active material of main body (main component).M in the above-mentioned general formula one or more elements for selecting from transition metal, x is the number of the condition of satisfied 0＜x＜1.And the metal complex that constitutes this electrode active material is amorphous.
Because the represented metal complex of above-mentioned general formula has less relatively electrochemical equivalent, can become the big material of theoretical capacity.And this noncrystalline material as metal complex is compared with the crystalline material, can become the electrode active material with better charge-discharge characteristic.By the kind electrode active material, for example can realize in the following effect at least, that is, improve first charge capacity (initial capacity), improve first discharge electricity amount (initial stage reversible capacity), reduce between initial capacity and the initial stage reversible capacity difference (irreversible capacity), reduce ratio (irreversible capacity/initial capacity) with respect to the irreversible capacity of initial capacity.As the concrete example of the M in the above-mentioned general formula, can be iron (Fe), vanadium (V) and titanium (Ti) etc.In addition, because above-mentioned metal complex is noncrystalline (unformed), so the x in the above-mentioned general formula can be a plurality of values.For example, can adopt the value of x is 1/2 (MBO
3), 1/3 (M
4B
2O
9), 1/4 (M
3BO
6) metal complex that waits.
A preferred version of electrode active material disclosed herein is that the M in the above-mentioned general formula is mainly Fe.That is to say, constitute roughly more than half among the M of this metal complex and be Fe.About 75 atom % or be Fe it more than among the preferred M, more preferably about 90 atom % or be Fe more than it among the M, further preferably M is essentially the situation of Fe.In for example above-mentioned formula M
2-2xB
2xO
3In x be that such metal complex can be by general formula Fe under 1/2 the situation
yM
1 1-yBO
3Represent.In this general formula, M
1Be one or more metallic elements of selecting the transition metal outside Fe (V, Ti etc.).In addition, y is for satisfying the number of 0.5≤y≤1.
Another preferred version of electrode active material disclosed herein is that the M in the above-mentioned general formula is mainly V.That is to say, constitute roughly more than half among the M of this metal complex and be V.About 75 atom % or be V it more than among the preferred M, 90 atom % or be V more than it more preferably from about, further preferably M is essentially the situation of V.In for example above-mentioned formula M
2-2xB
2xO
3In x be that such metal complex can be by general formula V under 1/2 the situation
zM
2 1-zBO
3Represent.In this general formula, M
2Be one or more metallic elements of selecting the transition metal outside V (Fe, Ti etc.).In addition, z is for satisfying the number of 0.5≤z≤1.
Because such electrode active material has shown better charge-discharge characteristic, thereby be suitable for electrode active material as secondary cell (being preferably electrolytical secondary cell) with non-water class.This electrode active material can be used as positive active material by other the selection (particularly constituting the electrode active material of the opposing party's electrode) of battery constituent material, also can be used as negative electrode active material.Usually, more preferably electrode active material of the present invention is used as negative electrode active material.M in above-mentioned general formula is under one or more the situation of element that is selected among Fe, V and the Ti, especially preferably with this electrode active material as negative electrode active material.
The invention provides a kind of anode for nonaqueous electrolyte secondary battery active material, it is with formula M
2-2xB
2xO
3(M is one or more the metallic element that is selected from the transition metal, 0＜x＜1) represented amorphous metal complex is a main component.This negative electrode active material for example can be suitable as the negative electrode active material of secondary lithium batteries.Such negative electrode active material for example can be the anode for nonaqueous electrolyte secondary battery active material that is made of the represented amorphous metal complex of above-mentioned general formula in fact.In addition, this negative electrode active material can also for, on basis, further comprise the anode for nonaqueous electrolyte secondary battery active material of lithium composition (lithium compound) by the represented amorphous metal complex of above-mentioned general formula.
In addition, the invention provides a kind of method of making above-mentioned such electrode active material, comprise following steps in a kind of scheme of this manufacture method: preparation process, in this step, prepare by formula M
2-2xB
2xO
3Represented metal complex; Amorphous materialization step makes above-mentioned metal complex amorphous materialization in this step.M in the above-mentioned general formula one or more elements for selecting from transition metal for example can be one or more elements of selecting from Fe, V and Ti, and x satisfy the condition of 0＜x＜1.
Here, so-called " amorphous materialization " is meant the processing of the degree of crystallinity that relatively reduces the prepared metal complex that goes out.Thus, the metal complex (i.e. metal complex before this amorphous materialization step) that is used to carry out above-mentioned noncrystalline materialization step is not limited in the material of substantial crystalline, also can contain amorphous part.In addition, the metal complex through after the noncrystalline materialization step can be essentially noncrystalline, also can contain the part of crystalline.In a word, as long as and through comparing before the above-mentioned amorphous materialization, relatively reduced to get final product through the degree of crystallinity of the metal complex after this noncrystalline materialization step.Typical situation is by this noncrystalline materialization step, to make the metal complex of substantial crystalline become substantial amorphous metal complex.
Processing as being comprised in above-mentioned noncrystalline materialization step for example can have the mechanically processing of hybrid metal complex compound.Can preferably adopt the processing of so-called mechanical lapping or mechanical grinding.Such processing method for example is suitable for the situation that M is mainly Fe.
The manufacture method of another kind of electrode active material disclosed herein wherein comprises following processing, that is, serve as that metal oxide and the boron oxide compound that constitutes metallic element (is typically B for the M that comprises with above-mentioned general formula
2O
3) mixture, with it from the molten condition quench cooled and it is solidified.Wherein, M one or more metallic elements for from transition metal (for example being Fe, V, Ti), selecting.This method is applicable to that preferably M is mainly Fe, M and is mainly metal complex of V etc.
A preferred version of above-mentioned manufacture method can for, the mixture that will also further contain lithium compound outward for the metal oxide that constitutes metallic element and above-mentioned boron oxide compound divided by above-mentioned M is from the molten condition quench cooled and it is solidified.As the lithium compound that is contained in the mixture, for example can be for from Li
2CO
3Deng lithium salts in one or more compounds of selecting.By adopting such lithium compound, can obtain being equivalent to being absorbed with in advance the electrode active material of the state of lithium.Can help reducing irreversible capacity thus.In addition, (the Li for example of the lithium compound by selecting to have the flux effect
2CO
3), can reduce the fusing point of said mixture.According to this programme, can realize at least one effect in the above-mentioned effect.
Any one above-mentioned electrode active material can be suitable as the constituent material of secondary cell (being typically lithium rechargeable battery).Such secondary cell, for example have: have any one above-mentioned electrode active material first electrode (negative or positive electrode), have second electrode (with the electrode of first electrode pairing, i.e. negative pole or positive pole) and the nonaqueous electrolytic that absorb and discharge cationic material.
According to a kind of rechargeable nonaqueous electrolytic battery provided by the invention, its negative pole has any one above-mentioned electrode active material.In addition, it is just having the material that absorbs and discharge alkali metal ion (preferred lithium ion).In addition, this secondary cell can have nonaqueous electrolytic.Because such secondary cell has the electrode active material that has improved charge-discharge characteristic, thereby can obtain better battery performance.
Description of drawings
Fig. 1 is the curve chart that is illustrated in the X ray diffracting spectrum of the sample of making in experimental example 1 and 2.
Fig. 2 is the curve chart that is illustrated in the X ray diffracting spectrum of the sample of making in experimental example 3 and 4.
Fig. 3 is the curve chart that is illustrated in the charging and discharging curve of the sample of making in experimental example 1 and 2.
Fig. 4 is the curve chart that is illustrated in the charging and discharging curve of the sample of making in the experimental example 4.
Fig. 5 is the curve chart that is illustrated in the charging and discharging curve of the sample of making in experimental example 3 and 4.
Fig. 6 is the curve chart that is illustrated in the charging and discharging curve of the sample of making in experimental example 3 and 4.
Embodiment
Below describe preferred implementation of the present invention in detail.Here, for implementing key element essential to the invention, the technology essential factor except the special content of recording and narrating in this specification is the technology essential factor that those skilled in the art can grasp based on prior art.The present invention is based on the technology general knowledge of the disclosed technology contents of this specification and this area and is implemented.
Electrode active material of the present invention is based on amorphous metal complex (transition metal boric acid complex) (main component).One or more noncrystalline material during this metal complex preference meets the following conditions in this way:
(1) average-size of crystallite is less than or equal to about 1000 dusts (preferably be less than or equal to about 100 dusts, be more preferably less than equal about 50 dusts);
Proportion (theoretical value) during (2) with complete crystallization is compared, the proportion of this metal complex about 3% or its above (more preferably about 5% or more than it);
(3) in X ray diffracting spectrum, do not observe the peak that is indicated as crystalline.That is to say that the typical case of the electrode active material of Ji Shuing is here, based on the electrode active material of transition metal boric acid complex, and this transition metal boric acid complex satisfies one or more in above-mentioned condition (1)～(3).For example, be preferably the metal complex that satisfies above-mentioned condition (3) at least.Here the electrode active material of Ji Shuing preference is, with amorphous transition metal boric acid complex electrode active material that is main component, and this amorphous transition metal boric acid complex satisfies one or more (particularly satisfying the transition metal boric acid complex of above-mentioned condition (3) at least) in above-mentioned condition (1)～(3), and for example this electrode active material can be the electrode active material that is made of above-mentioned amorphous pledge in fact.Here, for example can adopt to wait from the X-ray diffraction device (model is Rigaku RINT 2100HLR/PC) that Rigaku Denki Co., Ltd obtains and obtain above-mentioned X ray diffracting spectrum.Adopt the metal complex of noncrystalline degree higher (degree of crystallinity is low), the tendency that more can bring into play effect of the present invention is arranged.
This electrode active material can contain the lithium composition.The electrode active material that contains the lithium composition so also can be included in " with by formula M
2-2xB
2xO
3Represented amorphous metal complex is the electrode active material of main body " notion in.The above-mentioned lithium composition that contains for example can be Li
2CO
3For such electrode active material that contains the lithium composition, can further reduce its irreversible capacity.Here be not special qualification, but the M with respect to 1 mole
2-2xB
2xO
3, containing of lithium composition proportional (lithium atom convert mol ratio) can be in the scope of for example 5 moles or (typical case is 0.05～5 mole) below it, perhaps also can be at 2 moles or below it scope of (typical case is 0.1～2 mole).Electrode active material of the present invention because it has the noncrystalline structure, is suitable for making it to contain the lithium composition.
Such electrode active material for example can obtain by the following method, that is, and and to by formula M
2-2xB
2xO
3Represented transition metal boric acid complex carries out amorphous materialization and handles (degree of crystallinity of this complex compound is reduced).The manufacture method that is used for the metal complex of amorphous materialization processing is not particularly limited, and can adopt the manufacture method (solid state reaction, sintering process etc.) of general pottery.For example, can make by the following method and be used to carry out the metal complex that amorphous materialization is handled, promptly, prepare that to comprise with the M in the above-mentioned general formula serve as to constitute the oxide of metallic element or by adding in the compound (carbonate of M, nitrate, hydroxide) that heat energy obtains this oxide one or more, with they and boron compound (boric acid H for example
3BO
3) be mixed together and heat.The transition metal boric acid complex that obtains like this has the crystalline texture of typical calcite type.
As the method that makes metal complex amorphous materialization, for example can adopt and to carry out the method (mechanical milling method etc.) of mechanical mixture as the metal complex of process object.In addition, as other the method for amorphous materialization, can also list the method that above-mentioned metal complex is carried out quench cooled and it is solidified etc. from molten condition.For example, the metal complex of molten condition is dropped in the cryogenic media (frozen water etc.) and make its quench cooled and solidify.In addition, also can adopt so-called spray-on process.In addition, can repeat repeatedly such noncrystalline as required handles.In addition, also can make up the method for two kinds of employings or its above amorphous materialization as required.
As other method that obtains amorphous transition metal boric acid complex, can list following method, promptly, prepare that to comprise with the M in the above-mentioned general formula serve as to constitute the oxide of metallic element or by adding in the compound (carbonate of M, nitrate, hydroxide) that heat energy obtains this oxide one or more, and boron compound (B for example
2O
3Etc. such boron oxide compound) mixture, then with the method for this mixture from the molten condition quench solidification.As method, can adopt the method that fused mass is dropped into method in the cryogenic media, spray-on process etc. with this mixture (fused mass) quench solidification.Can also further carry out amorphous materialization by mechanical mixing (mechanical milling method etc.) to the coagulum that obtains like this handles.
Electrode active material of the present invention can have function as electrode active material by various cationic insertions and disengaging.As inserting the cation that breaks away from, for example can list the alkali metal ion of lithium ion, sodium ion, potassium ion and cesium ion etc.; The alkaline-earth metal ions of calcium ion and barium ions etc.; Magnesium ion, aluminium ion, silver ion, zinc ion; The TBuA ion, tetraethyl ammonium ion, tetramethyl ammonium, triethyl group ammonium methyl ion, the ammonium ion class of triethyl ammonium ion etc.; The imidazole salts ionic species of imidazole salts ion, ethyl-methyl imidazole salts ion etc.; Pyridinium ion, hydrogen ion, Si Yi Ji Phosphonium ion, tetramethyl phosphonium ion, tetraphenylphosphoniphenolate ion, triphenylsulfonium ion, triethyl group sulfonium cation etc.This wherein is preferably alkali metal ion, is preferably lithium ion especially.
This electrode active material both can also can be used as the negative pole of battery as the positive pole of battery.Under situation used as battery cathode, as the active material of the positive pole of its counter-electrodes, preferred use to comprise will insert the cation (being typically lithium ion) that breaks away from negative pole and the positive active material that constitutes.For example, can adopt with lithium and transition metal is the various lithium composite xoides that constitute metallic element.Can list lithium-cobalt oxide (Li for example as such lithium composite xoide
2CoO
2), lithium nickel type oxide (LiNiO for example
2), lithium manganese type oxide (LiMnO for example
2, LiNi
0.5Mn
1.5O
4, LiMn
2O
4) etc.Other positive active material as containing lithium can list LiFePO
4, LiCoPO
4Deng.In addition, TiO
2, V
2O
5, MoO
3Deng oxide, TiS
2, the electroconductive polymer of the sulfide of FeS etc., polyacetylene, polyparaphenylene, polyaniline, polypyrrole etc. etc. also can be used as positive active material.
On the other hand, with this electrode active material as under the situation of anode, the active material as the negative pole of its counter-electrodes can adopt the metal of Li, Mg, Al etc. or their alloy, perhaps can adopt to absorb and to discharge cationic material with carbon element.
Here, the M in the above-mentioned general formula is mainly Fe, V and the such electrode active material of Ti, perhaps one or more the electrode active material of M for mainly from Fe, V and Ti, selecting, and such electrode active material is especially suitable for use as negative electrode active material.
Electrode with electrode active material of the present invention can be suitable for the electrode as the secondary cell of coin shape, cylindrical shape, different shape such as square.For example, thus this electrode active material compression forming can be formed the electrode of ball shape etc.In addition, by with above-mentioned electrode active material attached on the formed collector body of electric conducting material by metal etc., can form the electrode of tabular or sheet.Such electrode except electrode active material of the present invention, can also contain one or more the material that comprises equally with the electrode with general electrode active material as required.The typical example of such material can list electric conducting material and bonding agent.Can use the material with carbon element of acetylene black etc. as electric conducting material.In addition, can use Kynoar (PVDF), polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropylene copolymer organic polymers such as (PVDF-HFP) as bonding agent.
As the nonaqueous electrolytic that secondary cell adopted, can use to comprise nonaqueous solvents and contain the material that can insert the cationic compound (supporting electrolyte) that breaks away from electrode active material.
Solvent as constituting nonaqueous electrolytic can use non-protonic solvents such as carbonates, ester class, ethers, nitrile, sulfone class, lactone, is not particularly limited in this here.For example can list propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid ethyl methyl esters, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, acetonitrile, propionitrile, oxolane, 2-methyltetrahydrofuran, two alkane, 1,3-dioxolanes, nitromethane, N, dinethylformamide, dimethyl sulfoxide (DMSO), sulfolane, gamma-butyrolacton etc.Not only can only use a kind of in so non-water kind solvent, can also be with wherein 2 kinds or use its above mixing.
In addition, as the supporting electrolyte that constitutes nonaqueous electrolytic,, for example under the situation of lithium rechargeable battery, can use to be selected from LiPF for containing with inserting and break away from the cationic compound of electrode active material
6, LiBF
4, LiN (CF
3SO
2)
2, LiCF
3SO
3, LiC
4F
9SO
3, LiC (CF
3SO
2)
2, LiClO
4Deng lithium compound (lithium salts) in one or more.
Below, example further describes the present invention by experiment, the qualification of the content that the present invention is not subjected in the experimental example being recorded and narrated.
The making of experimental example 1:Fe class crystalline sample
With Fe
2O
3And H
3BO
3Molar ratio with 1: 2 mixes mutually.They were fired 24 hours with 670 ℃ temperature in air, reburn with 750 ℃ temperature then and made 48 hours.By conventional method gains are pulverized and to be obtained sample (average grain diameter is 16.8 μ m), the sample of gained is carried out powder x-ray diffraction (XRD) measure.Measuring use can be from the X-ray diffraction device (model is " Rigaku RINT 2100HLR/PC ") of Rigaku Denki Co., Ltd's acquisition.Its result is illustrated among Fig. 1.
As shown in the figure, can from X ray diffracting spectrum, see tangible peak, illustrate that this sample is a crystalline.In addition, this pattern well with the data of login in ICDD match (ICDDNo.21-0423).Thus, can confirm that the resulting sample of this experimental example is the single-phase crystalline FeBO of calcite type
3
The making of the noncrystalline matter sample of experimental example 2:Fe class
Will be by mechanical milling method by experimental example 1 resulting crystalline FeBO
3Sample amorphous materialization.Adopt planetary ball mill (she makes Co., Ltd.'s system, model " LP-4/2 " by rattan) to carry out this mechanical lapping.That is to say, (zirconia by partially stabilizedization is made at the container of this ball mill, volume 80mL), in to put into diameter respectively with 100,15,4 and 2 s' ratio be the spheroid that the zirconia by partially stabilizedization of 3mm, 10mm, 15mm and 20mm is made, and then put into by experimental example 1 resulting crystalline sample FeBO
3(about 4g).Rotating condition is 200rpm.Whenever, carry out XRD determining through certain hour, begin to have passed through 48 hours from mechanical lapping after, whole peaks have all disappeared.The X ray diffracting spectrum of sample that will pass through 48 hours mechanical lapping is illustrated among Fig. 1 in the lump.So just make and come down to amorphous FeBO
3Sample (average grain diameter is about 2.98 μ M).This sample is equivalent to formula M
2-2xB
2xO
3In M be Fe, and x is 1/2 situation.
The making of experimental example 3:V class crystalline sample
With V
2O
3And H
3BO
3Mol ratio with 1: 2.1 is mixed.They were fired 24 hours the system of under 1200 ℃ temperature, reburning then 24 hours under 670 ℃ temperature.In order to prevent the oxidation of vanadium, above-mentioned sintering procedure is at the H that contains 5%
2Argon gas atmosphere under carry out.Same with experimental example 1, gains are pulverized, the sample of gained is carried out XRD determining.Its result is illustrated among Fig. 2.
As shown in the figure, in X ray diffracting spectrum, can see tangible peak, show that this sample is a crystalline.In addition, can judge from the result of XRD, this sample is the crystalline VBO with crystalline texture identical with experimental example 1 resulting sample (calcite type single-phase)
3
The making of experimental example 4:V class noncrystalline sample
In this experimental example,, make with by general formula VBO by fusion quench cooled method
3(be equivalent to formula M
2-2xB
2xO
3In M be V, x is 1/2 situation) represented metal complex is the noncrystalline sample of main body.
Will be as the V of about 3g in vanadium source
2O
3With B as about 1.4g in boron source
2O
3, and as the Li of about 1.5g of lithium compound
2CO
3Mixture (mol ratio is about 1: 1: 1), under 1500 ℃, carry out 15 minutes fusion.Then this fused mass is dropped in the frozen water and carry out quench cooled, use agate mortar to carry out powdered by pulverizer.Then resulting powder is carried out XRD determining.Measurement result is illustrated among Fig. 2 in the lump.As shown in the figure, in X ray diffracting spectrum, do not observe the peak.This illustrates this sample (V
2O
3-B
2O
3-Li
2CO
3Sample) is essentially noncrystalline.
In addition, even with mole mixture ratio be 1: 1 V
2O
3And B
2O
3Mixture be heated to 1600 ℃ and can not make its complete fusion, but by having added equimolar Li
2CO
3, can make mixture (is V
2O
3: B
2O
3: Li
2CO
3Mole mixture ratio be about 1: 1: 1 mixture) fusing point be reduced to 1500 ℃ or below it.More particularly, said mixture can be melted under about 1400～1500 ℃ temperature at least.
In addition, to experimental example 3 resulting crystalline VBO
3Sample and experimental example 3 have carried out mechanical lapping equally, even still residual in X ray diffracting spectrum after 48 hours mechanical lapping have a peak.
Experimental example 5: measure making with battery
Employing is measured at experimental example 1～4 resulting sample production and is used battery.
That is to say, mix following three kinds of compositions: as the about 0.25g of the sample of electrode active material, as the about 0.089g of acetylene black (AB) of electric conducting material and as the about 0.018g of the polytetrafluoroethylene (PTFE) of bonding agent (mass ratio is about 70: 25: 15).With this mixture compression forming is that discoid (the ball shape) of diameter 1.0cm, thick 0.5mm made the test electrode.Counter-electrodes adopts the lithium paper tinsel of diameter 1.5mm, thick 0.15mm.Dividing plate (separator) adopts the porous matter polyethylene sheets of diameter 22mm, thick 0.02mm.In addition, nonaqueous electrolytic adopts following solvent,, in the mixed solvent of 1: 1 volume ratio of ethylene carbonate (EC) and diethyl carbonate (DEC), is dissolved with LiPF with the concentration of about 1 mol that is
6Solvent.These inscapes are packed in the rustless steel container, thereby make the Coin-shape cell of thick 2mm, diameter 32mm (2032 type).
The evaluation of experimental example 6:Fe class sample
With adopting the mensuration of making making back placement 12 hours, after this, carry out the experiment that discharges and recharges of constant current under the following conditions with battery at the sample of experimental example 1 and experimental example 2.That is to say, with 0.1mA/cm
2Current density insert Li (charging) and reach 0.8V (Li/Li+ until cell voltage.Below same) till, then make Li break away from (discharge) till cell voltage reaches 3.0V with same current density.With the per minute is the voltage of unit record battery.Express the first charging and discharging curve of this moment among Fig. 3.
As shown in the figure, the initial capacity of the battery of the sample (crystalline) of employing experimental example 1 is about 700mAh/g, and irreversible capacity is about 390mAh/g, and the shared ratio of irreversible capacity is about 56% in the capacity in the early stage.Relative therewith, the battery of the sample (noncrystalline) of employing experimental example 2, initial capacity is about 530mAh/g, and irreversible capacity is about 180mAh/g, and the shared ratio of irreversible capacity is about 34% in the capacity in the early stage.Like this, compare with the crystalline sample of experimental example 1, the irreversible capacity of the noncrystalline sample of experimental example 2 has reduced to only about half of.In addition, irreversible capacity in the early stage in the capacity shared ratio also significantly descend.In addition, for the discharge curve in the process of inserting Li in the early stage, crystalline sample (experimental example 1) and noncrystalline sample (experimental example 2) all have the voltage flat near the 1.3V of same degree.
The evaluation of experimental example 7:V class sample
Employing is being made back placement 12 hours in the mensuration of the sample production of experimental example 3 and experimental example 4 with battery.After this, under each following condition, carry out the experiment that discharges and recharges of constant current.
Measure example 1
To adopting the noncrystalline sample (V of experimental example 4
2O
3-B
2O
3-Li
2CO
3Sample) mensuration applies the voltage of (charging) 4.5V with battery.Then, with 0.1mA/cm
2Current density insert Li till cell voltage reaches 0.2V, with same current density Li is broken away from till cell voltage reaches 2.5V, (be that the cyclical voltage scope is 0.2～2.5V).Express its charging and discharging curve (measuring example 1) at the epimere of Fig. 4.As shown in the figure, in the process that applies 4.5V voltage at first, do not observe the disengaging (characteristic curve rises to part till the 4.5V along the longitudinal axis) of Li in fact.This result shows, for employed Li when making the noncrystalline sample, its after charging process in still be present in (not disengaging) in the sample lattice.Can infer that its reason is, in the noncrystalline sample of experimental example 4, Li is caught on the dangling bonds in the glassy network, thereby has stoped the electrochemistry of Li to break away from.
In addition, omit the process that applies 4.5V voltage at first, with 0.1mA/cm
2Current density insert Li till cell voltage reaches 0.2V, with same current density Li being broken away from (is that the cyclical voltage scope is 0.2～2.5V) till cell voltage reaches 2.5V.As Fig. 4 hypomere is represented, obtain and measure the roughly the same charging and discharging curve (following mensuration example 4) of example 1.Owing to obtained such result, therefore in following mensuration example, begun to carry out charge and discharge cycles from the process of inserting Li.
Measure example 2,3
For the battery of the crystal sample that adopts experimental example 3, with 0.1mA/cm
2Current density insert Li till cell voltage reaches 0.2V, with same current density Li being broken away from (is that the cyclical voltage scope is 0.2～2.5V) till cell voltage reaches 2.5V.Express its charging and discharging curve (measuring example 2) at the epimere of Fig. 5.In this mensuration example, irreversible capacity (irreversible zone) in the early stage in the capacity shared ratio be 42%.
In addition, except the scope of cyclical voltage is 0.0～2.5V this point (promptly inserting Li until the point that reaches when measuring the lower cell voltage of example 3), and measures example 3 and discharge and recharge experiment equally.Its result is illustrated in Fig. 5 second section (measuring example 3).In this mensuration example, the ratio in irreversible zone is about 56%.
Measure example 4,5
Said determination example 4 is equivalent to the battery to the noncrystalline sample that adopts experimental example 4, and (current density and cyclical voltage scope) discharges and recharges the situation of experiment under the condition same with measuring example 3.For the ease of mutual comparative study measurement result, the 3rd segment table at Fig. 5 illustrates its charging and discharging curve (measuring example 4) once more.The ratio in the irreversible zone of this mensuration example is approximately 47%.In addition, irreversible capacity is about 400mAh/g.
In addition, for the battery of the noncrystalline thing sample that has adopted experimental example 4, under the condition same, discharge and recharge experiment with measuring example 4.Its result is illustrated in the hypomere (measuring example 5) of Fig. 5.The ratio in the irreversible zone of this mensuration example is approximately 37%.
From Fig. 5 represented result as can be seen, the cut-ff voltage when inserting with Li is that the situation of the more shallow circulation of 0.2V is compared (measuring example 2,4), cut-ff voltage is the more remarkable effect that the irreversible zone in the circulation more deeply (measuring example 3,5) of 0.0V dwindles.From second section of Fig. 5 and hypomere more as can be seen, for measuring example 3, measure irreversible capacity in the example 5 and roughly reduced the amount that is equivalent to 1Li (1Li be scaled capacity be equivalent to 244mAh/g), here.From this result as can be seen, the sample (V of example 4 by experiment
2O
3-B
2O
3-Li
2CO
3) in the Li that contained in advance, can bring into play the filling perforation effect of irreversible capacity.
Measure example 6,7
In the mensuration example 2～5 of above explanation, all be to be 0.1mA/cm in current density
2Condition under discharge and recharge experiment.Below further to current density is changed to 1.0mA/cm
2Situation study.
That is to say, for the battery of the crystalline sample that adopts experimental example 3, at 1.0mA/cm
2Current density and cyclical voltage scope be under the condition of 0.0～2.5V, discharge and recharge experiment (measure example 6).For the ease of mutual comparative study measurement result, express same sample at 0.1mA/cm at the epimere of Fig. 6 once more
2Current density under the charging and discharging curve (irreversible zone is approximately 56%) of the mensuration example 3 measured, second segment table at Fig. 6 is illustrated in 1.0mA/cm simultaneously
2Current density under the charging and discharging curve of the mensuration example 6 that determines.The ratio of measuring the irreversible zone in the example 6 is approximately 67%.
In addition, for the battery of the noncrystalline sample that adopts experimental example 4, example 6 is same with measuring, at 1.0mA/cm
2Current density and cyclical voltage scope be under the condition of 0.0～2.5V, discharge and recharge experiment (measure example 7).For the ease of mutual comparative study measurement result, the 3rd segment table at Fig. 6 illustrates same sample at 0.1mA/cm once more
2Current density under the charging and discharging curve (irreversible zone is approximately 37%) of the mensuration example 5 measured, express at 1.0mA/cm at the hypomere of Fig. 6 simultaneously
2Current density under the charging and discharging curve of the mensuration example 7 that determines.The ratio of measuring the irreversible zone in the example 7 is approximately 41%.
Result represented among Fig. 6 shows, not only at 0.1mA/cm
2Minimum current density under (measure example 3,5), and at 1.0mA/cm
2Under such high value current density (measure example 6,7), the effect of above-mentioned amorphous materialization and owing to the filling perforation effect that contains the irreversible capacity that the Li composition produces is in advance all significantly brought into play.For example, for the shared ratio in irreversible zone, be 0.1mA/cm in current density
2Condition under, the sample of experimental example 3 is approximately 56% (measuring example 3), in contrast to this, the sample of experimental example 4 is approximately 37% (measuring example 5), irreversible zone is dwindled significantly.In addition, at 1.0mA/cm
2Current density under, the ratio in the irreversible zone of the sample of experimental example 3 is approximately 67% (measuring example 6), in contrast to this, the ratio in the irreversible zone of the sample of experimental example 4 is approximately 41% (measuring example 7), even under such current density, also can see dwindling significantly of irreversible zone.
And then, mutual-through type V
2-2xB
2xO
3The different V class amorphous pledge of value of middle x is studied.That is to say,, make general formula V respectively according to the method identical with experimental example 4
2-2xB
2xO
3The value of middle x is 1/3 V class noncrystalline sample and general formula V
2-2xB
2xO
3The value of middle x is 1/4 V class noncrystalline sample.Adopt these samples, construct equally to measure with experimental example 5 and use battery.And, the same with the said determination example, for the mensuration battery that adopts each sample, at 0.1mA/cm
2Current density, and the cyclical voltage scope is to discharge and recharge experiment under the condition of 0.2～2.5V.Its result is, x is that 1/3 sample (is V
4B
2O
9) reversible capacity be about 450mA/cm
2, x is that 1/4 sample (is V
3BO
6) reversible capacity be about 500mA/cm
2
More than, though the specific embodiment of the present invention is had been described in detail, it only illustrates, and does not limit claim scope of the present invention.Be recorded in the technology of claim scope, be included in various distortion and the change carried out on the basis of above-mentioned illustrative concrete example.
In addition, for for the technology essential factor of being recorded and narrated in this specification and the accompanying drawing, it can be by bringing into play technique effect alone or in combination, the combination of being put down in writing in the claim when being not limited in application.In addition, for for the technology of being recorded and narrated in specification of the present invention and the accompanying drawing, it can be used for reaching simultaneously a plurality of purposes, also can be used to reach any one single goal wherein.
Claims (13)
1. electrode active material, it is with by formula M
2-2xB
2xO
3Represented amorphous metal complex is a main component, wherein, and M one or more metallic elements, and 0＜x＜1 for from transition metal, selecting.
2. electrode active material as claimed in claim 1, the M in the above-mentioned general formula is mainly iron.
3. electrode active material as claimed in claim 1, the M in the above-mentioned general formula is mainly vanadium.
4. electrode active material as claimed in claim 1, one or more during above-mentioned amorphous metal complex meets the following conditions:
(1) average-size of crystallite is smaller or equal to 1000 dusts;
(2) be entirely the crystalline situation under the theoretical value of proportion compare the ratio great 3% of this metal complex or more than it;
(3) in X ray diffracting spectrum, do not observe the peak that shows crystalline.
5. electrode active material as claimed in claim 1 further comprises lithium compound.
6. electrode active material as claimed in claim 1, it is used as the negative electrode active material of rechargeable nonaqueous electrolytic battery.
7. method of making electrode active material, this electrode active material is a main component with amorphous metal complex, described method comprises preparation with formula M
2-2xB
2xO
3The step of the metal complex that (M is one or more the metallic element that is selected from the transition metal, 0＜x＜1) is represented; With step with this metal complex amorphous materialization.
8. method as claimed in claim 7, the step of above-mentioned amorphous materialization comprises the processing that mechanically mixes above-mentioned metal complex.
9. method of making electrode active material, this electrode active material is with formula M
2-2xB
2xO
3(M is one or more the metallic element that is selected from the transition metal, 0＜x＜1) represented amorphous metal complex is a main component, described method is characterised in that, comprising preparation, to contain with the M in the above-mentioned general formula be the step that constitutes the mixture of the metal oxide of metallic element and boron oxide compound; With with the step of this mixture from the molten condition quench solidification.
10. method as claimed in claim 9, said mixture further contains lithium compound.
11. a rechargeable nonaqueous electrolytic battery, it has:
Negative pole, this negative pole has with formula M
2-2xB
2xO
3(M is one or more the metallic element that is selected from the transition metal, 0＜x＜1) represented amorphous metal complex is the electrode active material of main component;
Positive pole, this is just having the material that absorbs and discharge alkali metal ion; And
Nonaqueous electrolytic.
12. rechargeable nonaqueous electrolytic battery as claimed in claim 11, wherein, above-mentioned alkali metal is lithium.
13. a negative electrode active material that is used for rechargeable nonaqueous electrolytic battery, it is with by formula M
2-2xB
2xO
3Represented amorphous metal complex is a main component, wherein, and M one or more metallic elements, and 0＜x＜1 for from transition metal, selecting.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP373358/2003 | 2003-10-31 | ||
| JP2003373358A JP4543658B2 (en) | 2003-10-31 | 2003-10-31 | Electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1875507A true CN1875507A (en) | 2006-12-06 |
| CN100413126C CN100413126C (en) | 2008-08-20 |
Family
ID=34544091
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800323106A Expired - Fee Related CN100413126C (en) | 2003-10-31 | 2004-11-01 | Electrode active material and use thereof |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US7842419B2 (en) |
| EP (1) | EP1681739B1 (en) |
| JP (1) | JP4543658B2 (en) |
| KR (1) | KR100710520B1 (en) |
| CN (1) | CN100413126C (en) |
| CA (1) | CA2543721C (en) |
| WO (1) | WO2005043655A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101657919B (en) * | 2007-03-30 | 2012-07-04 | 丰田自动车株式会社 | Electrode active material and lithium secondary battery |
| CN104269529A (en) * | 2014-09-23 | 2015-01-07 | 中南大学 | Preparation method of lithium ion battery vanadium borate negative electrode material |
| CN104466126A (en) * | 2014-09-30 | 2015-03-25 | 中南大学 | Preparation method of lithium ion battery negative material VBO3/C |
| CN106159237A (en) * | 2016-08-26 | 2016-11-23 | 华南理工大学 | A kind of vanadio borate negative material and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4543658B2 (en) | 2003-10-31 | 2010-09-15 | トヨタ自動車株式会社 | Electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery |
| JP5099737B2 (en) * | 2005-06-30 | 2012-12-19 | 公益財団法人北九州産業学術推進機構 | Electrode active material, method for producing the same, and non-aqueous electrolyte secondary battery |
| JP5506358B2 (en) * | 2009-12-11 | 2014-05-28 | パナソニック株式会社 | Non-aqueous electrolyte battery active material and non-aqueous electrolyte battery |
| JP5553590B2 (en) * | 2009-12-11 | 2014-07-16 | パナソニック株式会社 | Non-aqueous electrolyte battery active material and non-aqueous electrolyte battery |
| CN102753480A (en) * | 2010-02-12 | 2012-10-24 | 旭硝子株式会社 | Boric acid compound, positive electrode for secondary battery, and method for manufacturing secondary battery |
| JP6046995B2 (en) * | 2012-11-29 | 2016-12-21 | 日本電信電話株式会社 | Method for manufacturing sodium secondary battery |
| CN103972491A (en) * | 2013-12-30 | 2014-08-06 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium-rich manganese-base anode material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6115941A (en) * | 1984-06-30 | 1986-01-24 | Res Dev Corp Of Japan | Ferromagnetic amorphous alloy containing oxygen and its manufacture |
| JPH08315858A (en) * | 1995-05-19 | 1996-11-29 | Fuji Photo Film Co Ltd | Nonaqueous secondary battery |
| JP3424722B2 (en) * | 1996-10-29 | 2003-07-07 | 日本電信電話株式会社 | Positive active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| JP3424725B2 (en) * | 1997-01-31 | 2003-07-07 | 日本電信電話株式会社 | Electrode active material for non-aqueous electrolyte secondary battery and alkali metal non-aqueous electrolyte secondary battery |
| JP3829410B2 (en) * | 1997-06-05 | 2006-10-04 | 宇部興産株式会社 | Anode material for non-aqueous battery and production method thereof |
| JP2003157841A (en) * | 2001-11-19 | 2003-05-30 | Central Glass Co Ltd | Electrode active material and battery using it |
| JP2003157842A (en) | 2001-11-19 | 2003-05-30 | Central Glass Co Ltd | Method for manufacturing electrode active material |
| JP4543658B2 (en) | 2003-10-31 | 2010-09-15 | トヨタ自動車株式会社 | Electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery |
-
2003
- 2003-10-31 JP JP2003373358A patent/JP4543658B2/en not_active Expired - Fee Related
-
2004
- 2004-11-01 EP EP04799531.1A patent/EP1681739B1/en not_active Expired - Fee Related
- 2004-11-01 KR KR1020067010674A patent/KR100710520B1/en not_active IP Right Cessation
- 2004-11-01 WO PCT/JP2004/016508 patent/WO2005043655A1/en active IP Right Grant
- 2004-11-01 CA CA2543721A patent/CA2543721C/en not_active Expired - Fee Related
- 2004-11-01 CN CNB2004800323106A patent/CN100413126C/en not_active Expired - Fee Related
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2006
- 2006-04-28 US US11/413,207 patent/US7842419B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101657919B (en) * | 2007-03-30 | 2012-07-04 | 丰田自动车株式会社 | Electrode active material and lithium secondary battery |
| US8703334B2 (en) | 2007-03-30 | 2014-04-22 | Kyushu University, National University Corporation | Amorphous electrode active material and lithium secondary battery |
| CN104269529A (en) * | 2014-09-23 | 2015-01-07 | 中南大学 | Preparation method of lithium ion battery vanadium borate negative electrode material |
| CN104269529B (en) * | 2014-09-23 | 2016-05-11 | 中南大学 | A kind of preparation method of lithium ion battery negative material boric acid vanadium |
| CN104466126A (en) * | 2014-09-30 | 2015-03-25 | 中南大学 | Preparation method of lithium ion battery negative material VBO3/C |
| CN104466126B (en) * | 2014-09-30 | 2016-08-31 | 中南大学 | A kind of preparation method of lithium ion battery negative material VBO3/C |
| CN106159237A (en) * | 2016-08-26 | 2016-11-23 | 华南理工大学 | A kind of vanadio borate negative material and preparation method thereof |
| CN106159237B (en) * | 2016-08-26 | 2020-02-18 | 华南理工大学 | Vanadium-based borate negative electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100710520B1 (en) | 2007-04-24 |
| CN100413126C (en) | 2008-08-20 |
| KR20060093127A (en) | 2006-08-23 |
| EP1681739B1 (en) | 2013-09-04 |
| JP2005135866A (en) | 2005-05-26 |
| CA2543721A1 (en) | 2005-05-12 |
| EP1681739A1 (en) | 2006-07-19 |
| US20060194104A1 (en) | 2006-08-31 |
| JP4543658B2 (en) | 2010-09-15 |
| US7842419B2 (en) | 2010-11-30 |
| CA2543721C (en) | 2012-06-05 |
| WO2005043655A1 (en) | 2005-05-12 |
| EP1681739A4 (en) | 2009-03-25 |
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